Nickel-Catalyzed Carboxylation of Aryl C-F Bonds with CO2

The C-F bond is the strongest single bond and it is one of the most challenging tasks to achieve the C-F bond functionalization. Here, we describe the first nickel-catalyzed selective defluorinative carboxylation of aryl C-F bonds with CO2. Various methyl carboxylates including partially fluorinated carboxylation compounds were obtained. Mechanistic studies reveal that the azanickelacycles might be vital intermediates in this transformation. This novel and straightforward carboxylation strategy will extend the scope of C-F bond functionalization and enhance the understanding of the reactivity of very stable bonds.

Automated summary

C-F bond, known for its strength, is challenging to functionalize. In this study, a nickel-catalyzed selective defluorinative carboxylation with CO2 was achieved, yielding various methyl carboxylates, including partially fluorinated compounds. Mechanistic studies suggest the involvement of azanickelacycles as vital intermediates. This novel and straightforward carboxylation strategy expands the scope of C-F bond functionalization and enhances the understanding of highly stable bond reactivity.